Phosphorus boron compounds



United States Patent 3,104,253 PHOSPHORUS BORON COMPOUNDS Theodor Reetz,Webster Groves, Mo., assignor to Monsanto Chemical Company, St. Louis,Mo., a corporation of Delaware No Drawing. Continuation of applicationSer. No. 807,327, Apr. 20, 1959. This application Sept. 18, 1961, Ser.No. 138,587

' 23 Claims. (Cl. 260-461) This invention relates to a new type ofphosphorus boron compounds and to the method of making the same. Inparticular, it is concerned with new compounds which may be designatedas hydrocarbon substituted phosphite borines, hydrocarbon substitutedphosphonite borines, and hydrocarbon substituted phosphinite borines.

Although hydrocarbon substituted phosphorus borines tree of oxygen areknown (see US. 2,860,167), the particular new compounds of thisinvention have not, prior to applicants discovery, been previouslydescribed. The new compounds of this invention are characterized asbeing relatively stable in comparison with some other known boronhydrogen compounds. For example, boron compounds like diborane,t-rimethylamine borine, and sodium borohydride react with dilute acidssuch as hydrochloric and sulfuric acids to form boric acid and hydrogen.However, most of the new phosphorus boron compounds of this invention donot react with dilute acids, but also are resistant towards iodine. Itis known that phosphites, phosphonites, and phosphinites react rapidlywith iodine to form the pentavalent phosphorus ester as follows:

wherein R is a hydrocarbon radical. The above reaction when carried outin the presence of ethanol and sodium bicarbonate has been utilized inthe present invention for the purpose of verifying the formation andpurity of the new compounds of this invention. In most cases thereaction products consumed either no iodine or only small amountsindicating either the absence of any of the starting trivalentphosphorus compounds or at most about 5 percent of the originaltrivalent phosphorus compounds, respectively.

It is therefore, an object of this invention to provide new oxygencontaining phosphorus boron compounds. A further object is to providephosphorus boron compounds containing oxygen which exhibit a'surprisingdegree of stability. A still further object is to provide a method forthe preparation of these new oxygen containing phosphorus boroncompounds. These and other objects of this invention will be apparentfrom the description that follows.

The new compounds of this invention have the follow ing structuralformula:

or E313 POh-Y o.-z where a, b, and 0 each have :a value from 0 to 1 andthe sum of i+b+c is at least 1. X, Y and Z are each hydrocarbonradicals. The term hydrocarbon radical as used in this patentapplication is to be construed in its broader sense in that the term notonly includes aliphatic, aryl, aralkyl, and cycloalkyl radicals but alsothose hydrocarbons which contain non-reactive substituents such as thehalogens like chlorine and fluorine. These substituents are considerednonreactive if they do not interfere with the formation of the newcompounds of this invention under the reaction conditions employed. In

Patented Sept. 17, 1963 accordance with this invention these newcompounds are prepared by reacting a compound of the structure:

o.-z where a, b, and c and the substituents X, Y and Z have the samemeaning as above with a compound of the class which is capable ofreleasing borine or diborane. Compounds ot this class include thetrialkylarnine borines such as trimethylamine borine, triethylamineborine, and the like; boron hydrides; and the metallic borohydrides suchas the alkali metal borohydrides, of which the borohydrides of sodium,lithium, and potassium are the preferred. Other metal borohydrides whichmay be used include those of aluminum and the alkali earth metals. Thetemperature at which compound (1) above is reacted with the borinereleasing compound will depend upon the nature of the latter compound.With the trialkylamine borines, temperatures from 20 C. to 120 C. andeven to 150 C. are more suitable. In the case of diborane lowertemperatures from 0 C. to -60 C. are more desirable. In the preferredembodiment where metallic borohydrides are employed, temperatures from40 C. to 100 C. may be used and usually the reaction is carried out inthe presence of an other as a solvent such as ethyl ether,tetrahydrofuran, dioxane, his (B-methoxyethyl) ether, and the like.Other suitable solvents include dimethylformamide, diethyl acetamide,and the like. Additional inert solvents maybe used providing theparticular metal borohydride employed is somewhat soluble therein.

It is to be noted that where the compound capable of releasing borine(EH is either a borane such as diborane (-I) or an amine horine such astrimethylamine borine (II), the reaction takes place readily. A trialkylphosphite is used by way of illustration although a phosphonite orphosphinite might have been used:

where R is an alkyl group.

On the other hand where the compound capable of releasing borine is analkali borohydride, the latter will not react with the phosphite,phosphonite, or phosphinite unless an additional reagent is used whichmay be (a) a carbonyl containing compound, (b) a proton donating orreleasing compound, or (c) a Lewis acid. Suitable carbonyl containingcompounds which can be used inwhere in each equation R is an alkylgroup.

The formation of the new phosphorus borine compounds of this inventionas shown by Equations III and IV above with only the partial reductionof the carbonyl compound is unexpected and surprising since metalborohydrides generally tend to react readily with carbonyl compounds andcarbon dioxide. It is obvious that other ket-ones such as diet-hyl'ketone, dihexyl ketone, and the like may have been used in the processof Equation IV above.

It has been also noted in those cases where the compound capable ofreleasing borine is a metallic borohydride that proton donating orreleasing compounds may be used in place of the carbonyl containingcompound to effect the reaction of the borohydride with the phosphite,phosphonite, or phosphinite compound. Example of proton donatingcompounds which may be effectively used are alcohols (V), phenols (VI),inorganic acids such as hydrobromic and hydrochloric (VII), and organicacids such as formic, acetic (VIII), butyric, valeric, and the like.Illustrative of this reaction are the following reactions in which atrialkyl phosphite is again used by way of illustration although aphosphonite or phosphinite might have been used:

Phenol Inorganic acid Organic acid where R in each instance is an alkylradical.

It will be apparent that trom Equations V-V-III inclusive that only onemole of the proton donating compound, whether an alcohol, phenol, oracid, is required to eifect the reaction. However, a small excess may beused even in the case of inorganic acids (VI I), since most of the newphosphorus compounds of this invention are resistant to dilute acids. Itwill also be evident that other phenols which may be employed inEquation VI above include xylenol, cresol, trimethylphenol, and thelike.

Finally it has also been discovered that Where the compound capable ofreleasing borine is a metallic borohydride, a further group of reagents,namely, Lewis acids, in addition to the (a) carbonyl type compounds and(b) the proton donating compounds noted above, can be used to efifectthe reaction of the metallic borohydride with the phosphite,phosphonite, or phosphinite compound. By way of example the followingreaction (IX) is given in which a trialkyl phosphite is again used toillustrate although a phosphonite or phosphinite might have been takenas an example of this reaction:

Lewis acid (IX) 3NaBH +4P(OR) +4BF 3NaBF '+4H BP(OR) where R is an alkylradical.

Representative of other Lewis acids besides BF which may be effectivelyemployed in this reaction are BCl A101 FeCl SnCl ZnCl and the like.

From the above it will be apparent that the method of preparing the newcompounds of this invention is of a general nature. The examples whichfollow are given to provide an indication of suitable reactants,solvents, and proportions of same as well as temperatures to be used inpreparing the new oxygen containing phosphorus boron compounds of thisinvention.

EXAMPLE I Trimethylphosphz'te BOrine H BP (OCH A mixture of 20.8 g. ofsodium borohydride (NaBH.;),

T riisopropylphosphite Borine H BP OC H 3 A. A mixture of 1.3 g. oftrimethylamineborine and 4.3 g. of triisopropylphosphite was heated in areaction vessel which was connected with a C0 cooled trap. Although someevolution of trimethylamine was observed at room temperature, pronouncedevolution of trimethylamine began at about 5060 C. The mixture wasgradually heated to 120 C. and finally to 140 C. for a short time. Theproduct was distilled and there was obtained 3.5 g. (88 percent oftheory) of triisopropylphosphite borine which boiled at 4242.5 C. at 0.1mm Hg.

B. When the above procedure was repeated with dimethylamine borineinstead of trimethylamine borine, there was obtained a reduced yield (57percent of theory), (which was probably attributable to side reactions).

EXAMPLE III Triethylphosphite Borine H BP OC H 3 A mixture of 11.34 g.of sodium borohydride (NaBH 50.0 g. of triethylphosphite, and 120 ml. oftetrahydrofuran was treated with CO at 2530 C. with vigorous stirring.The exothermic reaction which took place resulted in the absorption ofthe CO and was complete in about 3 hours. The reaction mixture was thenstirred at room temperature in the presence of CO for 5 additionalhours. The reaction mixture was filtered and the filtrate evaporatedunder vacuum conditions at 15 mm. Hg. There was obtained uponredistillation 39.7 g. (73 percent of theory) of pure triethylphosphiteborine, B.P. 106 C. at 22 mm. Hg.

EXAMPLE IV T ris( fl-Chloroethyl Phos'phite Borine H BP (OCH CH CI) 3 Amixture of 7.56 g. of sodium borohydride (NaBH 53.9 g. oftris(/8-ch1oroethyl) phosphite, and ml. of tetrahydrof-uran was treatedwith CO at 25-28 C. with vigorous stirring for 8 hours. The resultingreaction mixture was filtered and the filtrate evaporated. The residuewas washed several times with dilute HCl and twice with dilute aqueoussolution of Na S0 The resulting oil, which was separated and dried withNa SO amounting to 46.5 g. (82 percent of theory) was essentially puretris(fi-chloroethyl) phosphite borine.

EXAMPLE V T riphenylphosphite Borine H BP OC H 3 A mixture of 8.0 g. ofsodium borohydride (NaBH 62.0 g. of triphenyl phosphite, and ml. oftetrahydrofur-an was treated with CO at 28 C. with vigorous stirring for5 hours. The reaction mixture was then lightly diluted with water fromwhich an oil precipitated. The oil shortly thereafter crystallized.After drying the crystals in vacuum (25 mm. Hg), there was obtained 45.5g. (70 percent of theory) of crystalline triphenylphosphite borine, M.P.53-55 C.

EXAMPLE VI Dimethylphenylphosphonite Borine H313 P (O CHa): 'JaHu Amixture of 4.1 g. of sodium borohydride (NaBH 17.4 g. ofdimethylphenylphosphonite, and 100 ml. of.

tetrahydrofuran was treated with CO at 28-30 C. with vigorous stirringfor hours. Then the reaction mixture was filtered and the filtrateevaporated under reduced pressure. The residue was distilled and therewas obtained 11.0 g. (60 percent of theory) of dimethylphenylphosphoniteborine, B.P. 79.5-80.0 C. at 0.2 mm. Hg.

EXAMPLE VII Tri(n-Butyl) Phosphite Borine H BP( O'n-C H) 3 A mixture of3.9 g. of sodium borohydride (NaBH 25.0 g. of tr-i(n-.butyl) phosphite,and 60 ml. of tetrahydrofu-ran was treated with CO at 27-28 C. withvigorous stirring for 4 hours. The reaction mixture was then dilutedwith a large excess of water from which an oil separated. The oil wasfurther washed with dilute HCl and water. The oil was then dried with NaSO and subject to vacuum (0.5 mm. Hg) at 35 C. for 2 hours. There wasobtained 22.6 .g. (85 percent of theory) of tri(n-butyl) phosphiteborine.

EXAMPLE VIII T rz's( ,B-T rifluoroethyl Phosphite Borine I-I BP (OCH CF3 A mixture of 2.0 g. of sodium borohydride (NaBH 16.4 g. oftris(fi-trifluoroethyl) phosphite, and 60 ml. of tetrahydrofuran wastreated with CO at 28-30 C. with vigorous stirring for 3% hours. Thereaction mixture was then diluted with a large excess of Water fromwhich an oil separated. The oil was further washed with dilute HCl andwater. The oil was then dried with Na SO- and subject to vacuum (0.5 mm.Hg) at 30 C. to remove low boiler impurities. There was obtained 15.8 g.(92.0 percent of theory) of tris(/3-trifluoroethyl) phosphite borine.

EXAMPLE IX Tricyclohexylphosphite Borine a e 11)a V A mixture of 4.0 g.of sodium borohydride (NaBH 32.8 g. of tricyclohexyl phosphite, and 80ml. of tetrahydrofuran was treated with CO at 2830 C. with vigorousstirring for 3 /2 hours. The reaction mixture was then diluted with alarge excess of water from which an oil separated. The oil was furtherWashed'with dilute HCl and water. The oil was then dried with Na SO andsubject to vacuum (0.1 mm. Hg) at 30 C. to give 28.5 g. (83 percent oftheory) of tricyclohexylphosphite borine, M.P. 69.0 C. This new boroncompound unlike tricyclohexyl phosphite is not hydroscopic. (See A. E.Arbusov and F. G. Valitova, C. A. (1953) p. 10462.)

EXAMPLE X T ri(Tridecyl) Phosphite Borine 3 1a 27)a The procedure ofExample VII above was repeated except the reactants were 3.8 g. ofsodium borohydride, 67.7 g. of tri(tridecyl) phosphite, and 125 ml. oftetrahydrofuran. There was obtained 65.5 g. (94.0 percent of theory) oftri(tridecyl) phosphite borine.

EXAMPLE XI Ethyl Diphenylphosphinite Borine A mixture of 2.2 g. ofsodium borohydride (NaBH 12.5 g. of ethyl diphenylphosphinite, and 50ml. of tetrahydrofuran was treated with CO at 25-30 C. with vigorousstirring for 3 hours. The reaction mass was then diluted with a largeexcess of Water from which an oil was separated. The oil was furtherwashed with dilute HCl and water. The oil was then dried with Na S0 andsubjected to vacuum (0.1 mm. Hg) at 30 C. for 3 hours. There wasobtained 11.2 g. (77.0 percent of theory) of ethyl diphenylphosphiniteborine.

EXAMPLE XII Triethylphosphite Borine There was added 30.0 g. BF ET O ina dropwise manner to a mixture of 5.7 g. NaBH; and ml. oftetrahydrofuran at -30 C. with stirring within 70 minutes, followed byheating the reaction mixture under reflux conditions. The B H generatedin this way (JACS 75, 1953, pp. 202-7) was introduced into a solution of50 g. P(OEt) in 50 ml. tetrahydrofuran at 20 C. with stirring. Thereaction mixture was treated with dilute HCl, from which an oily productseparated. This was washed with water and dried with K 00 Finally it wassubjected to vacuum, 10 mm. Hg at 50 C., until the weight was constant.There was obtained 33.5 g. (92.5% of theory) essentially puretriethylphosphite borine.

EXAMPLE XIII Tri(n-heptyl) Phosphite Borine H 31 (OI1-'C7H15) 3 Theprocedure of Example VIII above was repeated except the reactants were5.5 g. of sodium borohydride, 37.6 g. of tri(n-heptyl) phosphite, and100.0 ml. of tetrahydrofuran. There was obtained 36.8 g. (95.0 percentof theory) of tri(n-heptyl) phosphite borine.

EXAMPLE XIV Triethylphosphite Borine H BP OC H 3 A mixture of 5.5 g. ofpotassium borohydride, 16.6 g. of [triethyl phosphite, and 50 ml. ofdimethylformamide was treated with CO at room temperature with vigorousstirring. The temperature of the reaction mass rose to 35 but was cooledto 30 C. and maintained at that temperature for one hour. The reactionmass was then stirred for 3 hours at room temperature. The resultingmixture was filtered and the filtrate evaporated at room temperatureunder vacuum conditions of 15 mm. Hg. There was obtained 13.5 g. (75.0percent of theory) of triethylphosphite borine.

EXAMPLE XV Triethylphospr'zite Borine A mixture of 3.8 g. of sodiumborohydride (NaBH 20.0 g. of triethylphosphite, and ml. oftetrahydrofuran did not react even on heating at reflux. However, when9.4 g. of phenol was gradually added a moderate formation of H tookplace. It is believed that the following reaction took place:

NaBH +HOC H +P(0C I-I 3 After 3 hours refluxing the reaction mixture wastreated several times with much water to dissolve the sodium phenolateand tetrahydrofuran. The insoluble portion,

.the triethyl phosphite borine was separated and washed with a diluteHCl to remove trialkyl phosphite. Finally the product was dried with NaCO and evacuated at 30 for 3 hours. There was obtained 13.6 g. (75% oftheory) of essentially pure triethyl phosphite borine.

'2 EXAMPLE XVI T riethylphosphite Borine A mixture of 20 g. of triethylphosphite, 3.8 g. of sodium borohydride (NaBHa), 10 g. oftrifiuoroethanol (F CH OH) and 100 g. of tetrahydrofuran was heated atreflux with stirring for 18 hours. A slow evolution of hydrogen tookplace which stopped after a few hours. The reaction mixture was thentreated with much dilute HCl. The product was separated from the waterlayer, dried with Na CO and subject to vacuum (10 mm. Hg at 25). Therewas obtained 4.3 g. (24% of theory) of triethylphosphite borine.

EXAMPLE XVII Triethylphosphite Borine A solution of 60 g. of glacialacetic acid in 20 ml. of tetrahydrofuran was added over a period of onehour to a mixture of 20 g. of triethyl phosphite, 3.89 g. of sodiumborohydride (NaBH and 100 ml. of tetrahydrofuran with stirring at 810 C.Strong evolution of H was observed as the acid was added. When anadditional gram of acid was added, only a small amount of H was notedindicating that the reaction was essentially completed. The reactionmixture was then heated at 50 C. for 45 minutes. Thereafter it wastreated with dilute HCl followed by washing with water. The product wasthen dried with Na CO and evacuated at 25 C. (10mm. Hg). There wasobtained 15.2 g. (88.5% of theory) of triethylphosphite borine.

EXAMPLE XVIII Triethylphosphite Borine A solution of 10.2 g. ofisovaleric acid in 30 m1. of tetrahydrofuran was added to a mixture of3.8 g. of sodium borohydride (NaBH 20 g. of triethyl phosphite, and 130ml. of tetrahydrofuran at 10 C. with stirring over a period of 1 /2hours. A strong evolution of H was noted. The reaction mixture was thenheated at reflux for 15 minutes and then several times treated withdilute NaOH to remove the unreacted valeric acid followed by treatmentwith dilute HCl to remove the excess of triethyl phosphite. Finally theproduct was Washed with water, separated, dried with Na SO and evacuatedat 25 C. (10 mm. Hg). There was obtained 13.6 g. (75.5% of theory) oftriethylphosphite borine.

EXAMPLE XIX T riisopropylphosphite Borine H3BP(OC3H7) 3 A solution of3.9 g. HCI dissolved in 30 ml. of tetrahydrofuran was added to a mixtureof 3.8 g. of sodium borohydride, 30 g. of triisopropyl phosphite, and 80ml. of tetrahydrofuran at -20 to -25 C. with stirring over a period of90 minutes. The reaction mixture was heated at 25 C. for one hour. Then10 g. of methanol was slowly added followed by the addition of 350 ml.of water with stirring to dissolve the excess of triisopropyl phosphitein the tetrahydrofuran. The organic layer was then Washed with water,dried with Na CO and subjected to vacuum at 45 C. (10 mg. Hg) until theweight was constant. There was obtained 15.0 g. (72 percent yield) oftriisopropylphosphite borine.

EXAMPLE XX T rz'isopropylphosphite Boriwe There was gradually added 6.2g. boric acid to a stirred mixture of 30 g. triisopropyl phosphite, 3.8g. NaBH and 80 ml. tetrahydrofuran at 18 within one hour. A strongevolution of H was observed. Then 10 ml. of H was slowly added. When theH evolution stopped, the reaction mixture was diluted with 350 ml.dilute HOl (about 0.2 n). The organic layer was washed with water, driedwith Na CO and subjected to 3 vacuum (10 mm. Hg) at 45 C. There wasobtained 7.3 g. (32.5% of theory) of triisopropylphosphite borine.

EXAMPLE XXI Triisopropylphosphite Borine To a mixture of 3.8 sodiumborohydride and ml. of. tetrahydrofuran at 40 C. there was added 6.2 g.of glacial acetic acid over a period of one hour. This mixture washeated slowly to 55 C. and maintained at this temperature for 10minutes. Then 30 g. of triisopropyl phosphite was added and theresulting reaction mixture was stirred at 50 C. for 2 hours. The organiclayer was washed with water, dried with Na CO and subjected to vacuumtreatment, as in the previous examples. There was obtained 17.9 g. (81%of theory) of triiscpropyl borine.

EXAMPLE XXII Triisopropylphosphite Borine A solution of 18.92 g.boronfluoride etherate BF (C H Odissolved in 20 ml. of tetrahydrofuranwas gradually added to a mixture of 3.8 g. of sodium borohydride, 80 ml.of tetrahydrofuran, and 30 g. of triisopropyl phosphite at 30 C. withstirring over a period of one hour. The reaction mixture was heated to50 C. and maintained at this temperature for 3 hours. Then 10 ml. waterwas slowly added. The reaction mixture was Worked up in the manner setforth in Example XXI. There was obtained 23.7 g. (87.2% of theory) oftriisopropylphosphite borine.

EXAMPLE XXIII T riisopropylphosphite Borine A mixture of 17.4 g. acetonewith 15 g. of water was gradually added to a stirred mixture of 3.8 g.NaBH 30 g. P(-OCSOC H and 80 ml. tetrahydrofuran at 18 over a period of1 /2 hours. The mixture was stirred at 5 0 C. for one hour and thenworked up as in Example XXI above. There Was obtained 16.0 g. (92% oftheory) of triisopropylphosphite borine.

Illustrative and representative of additional compounds which may beprepared in accordance with the process of this invention include:

Ethyl diethylphosphinite,

Propyl diethylphosphinite, Isopropyl diethylphosphinite,

Butyl diethylphosphinite,

Isobutyl diethylphosphinite,

Hexyl diethylphosphinite,

Heptyl diethylphosphinite,

Octyl diethylphosphinite,

Nonyl diethylphosphinite,

Decyl diethylphosphinite,

Hexyl diphenylphosphinite, Diethyl ethylphosphonite, Dimethylethylphosphonite, Dimethyl '(p-dimethylaminophenyl) phosphonite, Diallylphenylphosphonite,

Diallyl p-chlorophenylphosphonite, Dibutyl butylphosphonite, Diisobutylisobutylphosphonite, Diethyl propyl phosphonite, Dipropylpropylphosphonite, Diethyl butylphosphonite, Dipropyl butylphosphonite,and the like.

The new borines of this invention have considerable utility and are ofparticular value as a gasoline additive to prevent pre-ignition. By wayof example, tricresyl phosphate a well known pre-ignition suppressant,has been found to be only 60 percent as effective as certain of the newcompounds of this invention with respect to preventing pie-ignition. Inaddition the new compuonds of this invention find use as anti-oxidants,catalysts, in

. 9 oil additives, and as blowing agents in epoxy resins representativeof which would be the reaction product of bis(4-hydroxyphenyl)-2,2propane and epichlorohydrin.

While this invention has been described with respect to certainembodiments, it is not so limited, and it is to be understood thatvariations and modifications thereof obvious to those skilled in the artmay be made without departing from the spirit or scope of thisinvention.

. This application is a continuation of my copending application SerialNo. 807,327, filed April 20, 1959, now abandoned.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A compound of the formula where X, Y and Z are each selected from thegroup consisting of alkyl, haloalkyl, cycloalkyl, al lyl, monocyclicaromatic hydrocarbons and halogenated monocyclic aromatic hydrocarbons,a, b, and each has a value from zero to one and the sum of a+b+c is atleast one.

2. A compound of the formula Orr-X where X, Y and Z are each alkyl, a,b, and 0 each has'a value from zero to one and the sum of zt+b+c is atleast one.

3. A compound of the formula H313 P0bY OQZ where each of X, Y, and Z isa monocyclic aromatic hydrocarbon, a, b, and 0 each has a value fromzero to one and the sum of a+b+c is at least one.

4. Trimethylphosphite borine. 5. Triethylphosphite borine. 6.Tris-,G-chloroethylphosphite borine. 7. Triisopropylphosphite borine. 8.Triphenylphosphite borine. 9. Tricyclohexylphosphite borine. 10. Ethyldiphenylphosphinite borine. 11. Diethyl ethylphosphonite borine. 12. Theprocess for preparing a compound of the formula H 13 P-Ob-Y O -Z whereX, Y and Z are each selected from the group consisting of alkyl,haloal-kyl, cycloalkyl, allyl, monocyclic aromatic hydrocarbons andhalogenated monocyclic aromatic hydrocarbons, a, b, and 0 each has avalue from zero to one and the sum of a+b+c is at least one, whichcomprises reacting a compound of the, formula POb-Y 00-2 where a, b, c,X, Y, and Z have the same meaning as above with a borine group releasingcompound selected from the group consisting of alkylamine borines, boronhydrides and metal borohydrides.

13. The process of preparing a compound of the formula 10 Where X, Y andZ are each alkyl, a, b, and 0 each has a value from zero to one and thesum of a+b+c is at least one which comprises reacting a compound of theformula P0bY OZ where a, b, c, X, Y, and Z have the same meaning asabove with a borine grouprcleasing compound selected from the groupconsisting of alkylamine borines, boron hydrides and metal borohydrides.

14. The process of preparing a compound of the formula 11 B P-Ob-Y 0 -2where each or X, Y and Z is a monocyclic aromatic hydrocarbon, a, b, and0 each has a value from zero to one and the sum of a+b+c is at leastone, which comprises reacting a compound of the formula Orr-X P0b-Y O.=ZWhere a, b, c, X, Y, and Z have the same meaning as above with a borinegroup releasing compound selected from the group consisting ofalky-lamine borines, boron hydrides and metal boro'hydrides.

15. The process of preparing a compound of the formula 11 B PO Y OZwhere X, Y and Z are each selected from the gnoup consisting of alkyl,haloalkyl, cycloalkyl, allyl, monocyolic aromatic hydrocarbons andhalogenated monocyclic aromatic hydrocarbons, a, b, and 0 each has avalue from zero to IOHE and the sum of a+b+c is at least one, whichcomprises reacting a compound of the rformnla 0,-Z where a, b, c, X, Y,and Z have the same meaning as above with an alkylamine borine.

16. The process of preparing a compound of the formula H3BP-O| -Y 0.,-Zwhere X, Y and Z are each selected from the group consisting of alkyl,haloalkyl, cycloallryl, allyl, monocyolic aromatic hydrocarbons andhalogenated monocyclic aromatic hydrocarbons, a, b, and c each has avalue from zero to one and the sum of a+b+c is at least one, whichcomprises reacting a compound of the cforrnula PO -Y Orr-Z Where a, b,c, X, Y, and Z have the same meaning as above with a bonon hydride.

17. The process Oif preparing a compound or the dorrnula O r-X H BPO ,-Y

where X, Y, and Z are each selected .firorn the group consisting ofalkyl, thaloalkyl, cycloalkyl, allyl, monocyclic 1 1 aromatichydrocarbons and halogenated monocyclic aromatic hydrocarbons, a, b, andeach has a value (from zero to one and the sum of a+b+c is at least one,which comprises reacting a compound of the formula PObY OcZ

where a, b, c, X, Y, and Z have the same meaning as above with a metalborohydride and a carbonyl type compound of the class consisting ofcarbon dioxide and ketones.

18. The process of preparing a compound of the formula n"-X 11 B P--0bYwhere X, Y, and Z are each selected from the group consisting of alkyl,haloalkyl, cycloalkyl, allyl, monocyclic aromatic hydrocarbons andhalogenated monocyclic aromatic hydrocarbons, a, b, and 0 each has avalue from zero to one and the sum of a-l-b-l-c is at least one, whichcomprises reacting a compound of the formula POb-Y where a, b, c, X, Y,and Z have the same meaning as above with a metal borohydride and anacid type compound selected from the group consisting of [fatty acidshaving 1 to 5 carbon atoms, mineral and Lewis type acids, and phenols.

19. The process of preparing a compound of the formula Orr-X HaBP-O -Y0.,-Z where X, Y, and Z are selected from the group consisting of alkyl,haloalkyl, cycloalkyl, allyl, monocyclic aromatic hydrocarbons andhalogenated monocyclic aromatic hydrocarbons, a, b, and 0 each has avalue from zero to one and the sum of a+b+c is at least one whichcomprises reacting a compound of the formula P-Ob-Y where a, b, c, X, Y,and Z have the same meaning as above with trimelthylamine borine.

20. The process of preparing a compound of the formula H313 P--Ob-'Ywhere X, Y, and Z are each selected from the group consisting of alkyl,haloalkyl, cycloalkyl, allyl, monocyclic aromatic hydrocarbons andhalogenated monocyclic aromatic hydrocarbons, a, b, and c each has avalue from zero to one and the sum of a+b+c is at least one whichcomprises reacting a compound of the formula where a, b, c. X, Y, and Zhave the same meaning as above with triethylamine borine.

12. 21. The process of preparing a compound of the formula H313 P-Ob-Ywhere X, Y, and Z are each selected from the group consisting of alkyl,haloalkyl, cycloalkyl, allyl, monocyclic aromatic hydrocarbons andhalogenated monocyclic aromatic hydrocarbons, a, b, and c each has avalue from Zero to one and the sum of a+b+c is at least one whichcomprises reacting a compound of the formula P-Ob-Y Where a, b, c. X, Y,and Z have the same meaning as above with diborane.

22. The process of preparing a compound of the formula 113B P-Ob-Y oc-zWhere X, Y, and Z are each selected from the group consisting of alkyl,haloalkyl, cycloalkyl, allyl, monocyclic aromatic hydrocarbons andhalogenated monocyclic aromatic hydrocarbons, a, b, and 0 each has avalue from zero to one and the sum of a+b+c is at least one whichcomprises reacting a compound of the formula where a, b, c. X, Y, and Zhave the same meaning as above with sodium borohydride and carbondioxide in the presence of a solvent.

23. The process of preparing a compound of the formula where X, Y, and Zare each selected from the group consisting of alkyl, haloalkyl,cycloalkyl, allyl, monocyclic aromatic hydrocarbons and halogenatedmonocyclic aromatic hydrocarbons, a, b, and 0 each has a value from zeroto one and the sum of a+b +c is at least one which comprises reacting acompound of the formula where a, [7, c. X, Y, and Z have the samemeaning as above with potassium borohydride and carbon dioxide in thepresence of a solvent.

References Cited in the file of this patent UNITED STATES PATENTS2,844,454 Birum July 22, 1958 2,921,096 Burg et a1 Jan. 12, 19602,925,440 Burg et al Feb. 16, 1960 2,926,194 Burg et a1 Feb. 23, 1960OTHER REFERENCES Graham et al.: J. Inorg. Nuclear Chem, vol. 3, pp.164-169, 1956.

Reetz, J. Am. Chem. Soc, vol. 82, No. 19, Oct. 5, 1960, pp. 5039-5042.

12. THE PROCESS FOR PREPARING A COMPOUND OF THE FORMULA